CN117700657A - Poly (4-aryl) piperidine polymer, preparation method and prepared anion exchange membrane - Google Patents
Poly (4-aryl) piperidine polymer, preparation method and prepared anion exchange membrane Download PDFInfo
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- CN117700657A CN117700657A CN202311381163.4A CN202311381163A CN117700657A CN 117700657 A CN117700657 A CN 117700657A CN 202311381163 A CN202311381163 A CN 202311381163A CN 117700657 A CN117700657 A CN 117700657A
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- Prior art keywords
- aryl
- piperidine
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- polymer
- poly
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 229920000642 polymer Polymers 0.000 title claims abstract description 150
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 100
- 239000000243 solution Substances 0.000 claims description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 44
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000012528 membrane Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 19
- 229920006254 polymer film Polymers 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 150000002576 ketones Chemical class 0.000 claims description 12
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000005956 quaternization reaction Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XJCUTBWYGIBFSL-UHFFFAOYSA-N C(C)C(=O)CC.N1CCCCC1 Chemical compound C(C)C(=O)CC.N1CCCCC1 XJCUTBWYGIBFSL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical group FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- -1 quaternary ammonium salt cations Chemical class 0.000 abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000126 substance Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000012074 organic phase Substances 0.000 description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 229920001519 homopolymer Polymers 0.000 description 25
- 238000003756 stirring Methods 0.000 description 23
- 239000005457 ice water Substances 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 230000008961 swelling Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229920000554 ionomer Polymers 0.000 description 9
- IECMOFZIMWVOAS-UHFFFAOYSA-N 4,4-dimethylpiperidine Chemical compound CC1(C)CCNCC1 IECMOFZIMWVOAS-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 7
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical group CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 7
- BEZIGJBIZRSSCG-UHFFFAOYSA-N 2,2,2-trifluoro-1-(1-methylpiperidin-4-yl)ethanone Chemical compound CN1CCC(C(=O)C(F)(F)F)CC1 BEZIGJBIZRSSCG-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229930184652 p-Terphenyl Natural products 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000007867 post-reaction treatment Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000000935 solvent evaporation Methods 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- KEBFNCSZEIBHEV-UHFFFAOYSA-N 1-benzyl-4,4-dimethylpiperidine Chemical compound C1CC(C)(C)CCN1CC1=CC=CC=C1 KEBFNCSZEIBHEV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229930015704 phenylpropanoid Natural products 0.000 description 3
- 150000002995 phenylpropanoid derivatives Chemical class 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 2
- QJXCFMJTJYCLFG-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzaldehyde Chemical compound FC1=C(F)C(F)=C(C=O)C(F)=C1F QJXCFMJTJYCLFG-UHFFFAOYSA-N 0.000 description 2
- OXIVWFPBZQTUTR-UHFFFAOYSA-N 2-benzyl-1-methylpiperidine Chemical compound CN1CCCCC1CC1=CC=CC=C1 OXIVWFPBZQTUTR-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000008378 aryl ethers Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 229920002480 polybenzimidazole Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VUQMOERHEHTWPE-UHFFFAOYSA-N 1-ethylpiperidin-2-one Chemical compound CCN1CCCCC1=O VUQMOERHEHTWPE-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YFNOTMRKVGZZNF-UHFFFAOYSA-N 2-piperidin-1-ium-4-ylacetate Chemical compound OC(=O)CC1CCNCC1 YFNOTMRKVGZZNF-UHFFFAOYSA-N 0.000 description 1
- HASRFXGIJALRRB-UHFFFAOYSA-N 4-(3-phenylpropyl)piperidine Chemical compound C=1C=CC=CC=1CCCC1CCNCC1 HASRFXGIJALRRB-UHFFFAOYSA-N 0.000 description 1
- ABGXADJDTPFFSZ-UHFFFAOYSA-N 4-benzylpiperidine Chemical compound C=1C=CC=CC=1CC1CCNCC1 ABGXADJDTPFFSZ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- JIDUBFKLNRRLDT-UHFFFAOYSA-N [Ru].[Pt].[C] Chemical compound [Ru].[Pt].[C] JIDUBFKLNRRLDT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- SRJOCJYGOFTFLH-UHFFFAOYSA-N isonipecotic acid Chemical compound OC(=O)C1CCNCC1 SRJOCJYGOFTFLH-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of hydrogen production by water electrolysis and fuel cells, and particularly relates to a poly (4-aryl) piperidine polymer, a high-stability anion exchange membrane prepared from the poly (4-aryl) piperidine polymer, and a preparation method and application of the poly (4-aryl) piperidine polymer. According to the poly (4-aryl) piperidine polymer and the anion exchange membrane, the skeleton structure of an all-carbon main chain is adopted, the piperidine ring is far away from a rigid main chain skeleton to enhance the ion mobility and improve the alkaline stability of quaternary ammonium salt cations, and the polymer is modified by copolymerization with a hydrophobic unit to form the polymer with an ultra-high stable chemical structure, so that the anion exchange membrane with the ultra-high stability is prepared.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis and fuel cells, and particularly relates to a poly (4-aryl) piperidine polymer, a high-stability anion exchange membrane prepared from the poly (4-aryl) piperidine polymer, and a preparation method and application of the poly (4-aryl) piperidine polymer.
Background
With the growing global energy crisis and environmental concerns, human society is urgently required sustainable green energy solutions to reduce reliance on fossil fuel combustion. Although most renewable energy sources such as solar energy, wind energy and other resources are rich, the application of the renewable energy sources is limited by seasons and regions, the renewable energy sources have strong intermittence and cannot be integrated into a national power grid, and the utilization rate of the resources is greatly reduced. The recycling of hydrogen is a potential solution to this problem by combining such renewable resources with efficient energy storage technologies.
Hydrogen is a clean and high-energy fuel, and electricity converted from renewable energy sources such as solar energy can be efficiently stored as chemical energy by producing hydrogen through electrolysis of water. The reverse reaction of the water electrolysis is applicable to the efficient power generation of a fuel cell, hydrogen is consumed in the process, and only water is generated as a byproduct, so that a green low-carbon cyclic development system is realized. Thus, the combination of the two techniques described above constitutes a key to hydrogen economy.
At present, technologies of water electrolysis hydrogen production and fuel cells are rapidly developing, and are expected to become a key technology for supporting development of high-proportion new energy sources in the future and constructing a hydrogen-electricity cooperative pattern. Taking the water electrolysis hydrogen production technology as an example, three common water electrolysis hydrogen production technologies currently exist, including an alkaline aqueous solution electrolysis technology (ALK), a cation exchange membrane electrolysis water technology (PEM-WE) and an anion exchange membrane electrolysis water technology (AEM-WE). Studies have shown that AEM-WE has the advantages of low cost and faster electrode reactions than PEM-WE and ALK. Currently, the main technical bottleneck of AEM-WE is its insufficient performance and lifetime, which includes the lack of high performance ionomers and anion exchange membranes. Among other things, ionomers can be used as catalyst binders in battery electrodes. The anion exchange membrane separates the two ends of the electrode from the reactant gas and conducts hydroxide ions between the electrodes. High conductivity is the basis for the function of the materials described above, and the requirements of high performance AEM-WE devices for ionomers and ion exchange membranes include their long term stability in addition to high conductivity. In alkaline environments with high hydroxide ion concentrations, particularly at high temperatures (60-90 ℃), ionomers and anion exchange membranes are susceptible to chemical degradation and perforation. Since this degradation process is irreversible, prolonged operation can degrade battery performance and thus cause electrode shorting, ultimately leading to device failure. Therefore, developing a class of ionomers and anion exchange membranes with high ionic conductivity, high mechanical stability, and high alkaline stability can greatly extend the useful life of AEM-WE. In addition, the two materials are also widely applied to new energy electrochemical devices in the fields of electrodialysis, carbon dioxide reduction, flow batteries and the like.
Currently, new AEMs for AEM-WE or AEM-FCs have been developed, including most polymer backbones such as Polyetheretherketone (PEEK), polysulfone (PSF), polyphenylene oxide (PPO), polybenzimidazole (PBI), and cationic groups (tetraalkylammonium, imidazolium, phosphonium, and organometallic cations). The results of the study show that the aromatic ether linked polymer backbone and benzyltrimethylammonium cation are susceptible to OH - The attack of (2) causes backbone breakage and cation loss, severely impairing the durability of the AEM. The recently developed novel AEM of the poly (aryl piperidine) copolymer synthesized by using electron-rich phenyl monomers and piperidone as raw materials and adopting super-strong acid for catalytic polycondensation has the advantages that the basic stability of the AEM is improved due to the fact that the aryl ether skeleton and the cyclic quaternary ammonium salt structure are not included, but the stability of the piperidine ring is greatly reduced due to the fact that the structural deformation and the ring strain relaxation of the piperidine ring are caused by the rigid main chain, and the mechanical stability of the AEM is reduced.
In summary, the AEM developed at present still has a plurality of structural defects, so that the AEM still cannot meet the requirements of special application scenes, and particularly in large-size large-scale industrial application, the durability and efficiency of AEM-WE and AEM-FCs devices are directly determined by higher alkaline stability. Therefore, there is a need in the art to develop an AEM that combines excellent mechanical strength, high ionic conductivity and ultra-high chemical stability, effectively pushing the mass production and industrialization of AEM-WE and AEM-FC.
Disclosure of Invention
Therefore, the first technical problem to be solved by the invention is to provide a poly (4-aryl) piperidine polymer and an OH-type quaternized poly (4-aryl) piperidine polymer, wherein the poly (4-aryl) piperidine polymer is prepared by carrying out polycondensation reaction on an electron-rich linear benzene ring monomer and an N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine monomer structure to obtain a skeleton structure of an all-carbon main chain, and meanwhile, the 4 position of an N-methyl piperidine ring is connected with the main chain through a single bond, so that the ring tension of the piperidine ring is obviously reduced, and the chemical structural stability of AEM is further improved. As shown in the example, the copolymer has lower water absorption rate and swelling rate by using the copolymer and hydrophobic units, can further improve the mechanical stability and the electric conductivity of AEM, and can be used for preparing anion exchange membranes with high stability;
the second technical problem to be solved by the invention is to provide an anion exchange membrane prepared based on the poly (4-aryl) piperidine polymer, wherein the anion exchange membrane has ultrahigh chemical stability, structural stability, excellent conductivity and ion conductivity, and excellent performance in AEM-WE, AEMFCs and other applications;
the third technical problem to be solved by the present invention is to provide a method for preparing the poly (4-aryl) piperidine polymer and an anion exchange membrane.
In order to solve the technical problems, the poly (4-aryl) piperidine polymer comprises a piperidine structure polymerization unit with a structure shown in the following formula (P1);
wherein,
a is 0 or 1;
x is an integer of 0 to 10;
ar is a phenyl structural monomer with a linear structure.
Specifically, in the poly (4-aryl) piperidine polymer, when a=0, the poly (4-aryl) piperidine polymer is a polymer including an N-methyl-4- (trifluoro-2, 2-diarylalkyl) piperidine structure, as shown in the following formula (P1 a); when a=1, the poly (4-aryl) piperidine polymer is a polymer comprising an N-methyl-4- (4- (trifluoro-2, 2-diarylethyl) phenylalkyl) piperidine structure, as shown in formula (P1 b) below.
Specifically, the poly (4-aryl) piperidine polymer further comprises a linear structure polymerization unit having a structure represented by the following formula (P2);
wherein,
ar is a phenyl structural monomer with a linear structure;
the R is 1 Is a hydrophobic copolymerized unit.
Specifically, the poly (4-aryl) piperidine polymer has a structure shown in the following formula (P):
wherein,
a is 0 or 1;
x is an integer of 0 to 10;
ar is a phenyl structural monomer with a linear structure;
The R is 1 Is a hydrophobic copolymerized unit.
Specifically, the poly (4-aryl) piperidine polymer comprises a piperidine structure polymeric unit and a linear structure polymeric unit; wherein,
y n mole ratio,%;
y m mole ratio,%, of polymerized units in the polymer for the linear structure;
wherein y is n 60% -100%; y is m 0% -40% and y n +y m ＝100％。
Specifically, the poly (4-aryl) piperidine polymer, wherein in Ar, the phenyl structural monomer comprises 2-4 substituted or unsubstituted phenyl monomers which are connected in a linear manner;
preferably, in the phenyl structural monomers, each phenyl monomer is connected by a single bond, an unsaturated bond or forms a linear annular structure;
preferably, the Ar comprises a diphenyl-substituted linear aromatic hydrocarbon;
preferably, the Ar comprises at least one of the following structural phenyl monomers:
wherein R is 2 Are alkyl chains C1-C10.
Wherein (a) is biphenyl, (b) is p-terphenyl, (c) is tetraterphenyl, (d) is m-terphenyl, (e) is diphenylethane, (f) is trans-1, 2-stilbene, (g) is cis-1, 2-stilbene, and (h) is dialkyl-substituted fluorene (R) 2 Is an alkyl chain C1-C10), (i) is N-R 2 Carbazole (R) 2 Is alkyl chain C1-C10), (j) is dibenzo-18-crown-6, (k) is 1,1' -binaphthyl, (l) is diphenyl ether, (m) is xanthene, (n) is 6,6' -dimethoxy-3, 3' -tetramethyl-1, 1' -spiroindan, (o) is 9,9' -dialkyl substituted-2, 7-diphenylfluorene (R) 2 Are alkyl chains C1-C10).
Specifically, the poly (4-aryl) piperidine polymer, R 1 Wherein the hydrophobic copolymerization unit comprises a hydrophobic monomer containing an electron withdrawing group structure;
preferably, the hydrophobic co-polymer unit comprises a substituted or unsubstituted aromatic ring hydrophobic monomer, a substituted or unsubstituted saturated aliphatic hydrophobic monomer, or a substituted or unsubstituted ketone hydrophobic monomer;
preferably, the hydrophobic co-polymer unit is selected from monomers comprising trifluoromethyl, carbonyl and/or pentafluorobenzene structures;
preferably, said R 1 Comprises the following structureAt least one of the hydrophobic co-units of (a):
wherein R is 3 Is alkyl; r is R 4 Is hydrogen, an alkyl chain or an aryl group;
wherein (a) is trifluoroacetophenone and (b) is trifluoroacetyl compound (R) 3 Is alkyl), (c) is 2, 3-butanedione, (d) is N-R 4 Isatin (R) 4 Hydrogen atom, alkyl chain and aryl group), (e) pentafluorobenzaldehyde;
Preferably, the hydrophobic co-units are formed by the reaction of corresponding ketone monomers.
The invention also discloses a method for preparing the poly (4-aryl) piperidine polymer, which is characterized by comprising the steps of taking a phenyl structural monomer Ar, (4-aryl) piperidine monomer with a linear structure and a hydrophobic copolymerization unit R according to the selected structure of the poly (4-aryl) piperidine polymer 1 Adding the corresponding ketone monomer into a first solvent for mixing, carrying out polymerization reaction in the presence of a first catalyst, adding a reaction solution into a second solvent for mixing, and collecting a precipitated polymer;
the (4-aryl) piperidine monomer comprises N-methyl-4-trifluoroalkyl ketone piperidine or N-methyl-4-trifluoroaryl ethyl ketone piperidine.
Specifically, the preparation method of the poly (4-aryl) piperidine polymer comprises the following steps:
the molar ratio of the phenyl structural monomer Ar with the linear structure to the (4-aryl) piperidine monomer is 1: (1-1.5); and/or the number of the groups of groups,
the hydrophobic copolymerization unit R 1 The molar ratio of the corresponding ketone monomer to the (4-aryl) piperidine monomer is (0-0.5): 1, a step of; and/or the number of the groups of groups,
the first solvent comprises at least one of dichloromethane, chloroform or tetrahydrofuran; and/or the number of the groups of groups,
The second solvent comprises at least one of ethyl acetate, methanol, ethanol, diethyl ether, tetrahydrofuran or acetone; and/or the number of the groups of groups,
the volume ratio of the first solvent to the second solvent is 1: (10-30); and/or the number of the groups of groups,
the (4-aryl) piperidine monomer is added in an amount of 10-22.5mmol of the (4-aryl) piperidine monomer per 10-15mL of the first solvent based on the amount of the first solvent added; and/or the number of the groups of groups,
the first catalyst comprises trifluoroacetic acid (TFA) and/or trifluoromethanesulfonic acid (TFSA); wherein,
the molar ratio of the trifluoroacetic acid to the (4-aryl) piperidine monomer is (1-2): 1, a step of; and/or the number of the groups of groups,
the molar ratio of the trifluoromethanesulfonic acid to the (4-aryl) piperidine monomer is (10-20): 1, a step of; and/or the number of the groups of groups,
said step (1) further comprising the step of washing and/or drying said polymer; wherein,
the washing step comprises the step of adding a first alkali liquor for washing and the step of adding the first alkali liquor for washing; preferably, the primary lye comprises K 2 CO 3 KOH, naOH or NaHCO 3 At least one of the solutions, preferably at a concentration of 0.5-2.0M; and/or the number of the groups of groups,
the drying step includes a step of vacuum drying at 60-80 ℃.
The invention also discloses a (4-aryl) piperidine monomer for preparing the poly (4-aryl) piperidine polymer, wherein the monomer comprises a trifluoroacetyl group and an N-methylpiperidine ring group, and the formula (M) is shown as the following, a=0 or 1, and x is an integer of 0-10. The (4-aryl) piperidine monomer includes N-methyl-4-trifluoroalkyl ketopiperidine (a=0) or N-methyl-4-trifluoroaryl ethyl ketopiperidine (a=1).
The invention also discloses a preparation method of the N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine monomer structure, which comprises the steps of selecting proper raw materials, trifluoro acetic anhydride and a first base or a first acid to be added into a first solvent for mixed reaction according to the selected structure of the N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine, and carrying out post-treatment; collecting the crude product, adding a second solvent, and reacting under the condition of a second acid or a second alkali to obtain corresponding salt or amine, and carrying out post-treatment; the final salt or amine is reacted with alkyl groups under the action of a first catalyst under the conditions of a third acid and a first aldehyde, and is post-treated.
Specifically, the preparation method of the N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine monomer structure comprises the following steps:
the molar ratio of the raw materials to the trifluoroacetic anhydride is 1 (1.1-5.6); and/or the number of the groups of groups,
the molar ratio of the trifluoroacetic anhydride to the first base or first acid is 1: (1-1.4); and/or the number of the groups of groups,
the first base comprises N, N-diisopropylethylamine, pyridine, triethylamine or 4-dimethylaminopyridine; and/or the number of the groups of groups,
the first acid comprises; zinc chloride, aluminum trichloride, ferric trichloride or boron trifluoride; and/or the number of the groups of groups,
The molar ratio of the starting material to the first solvent is 1: (1-4); and/or the number of the groups of groups,
the first solvent comprises at least one of dichloromethane, chloroform, toluene or tetrahydrofuran; and/or the number of the groups of groups,
the molar ratio of the crude product to the second solvent was 1: (1-10); and/or the number of the groups of groups,
the second solvent comprises at least one of water, methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or acetone; and/or the number of the groups of groups,
the molar ratio of crude product and second acid/second base was 1: (50-100); and/or the number of the groups of groups,
the second acid comprises; hydrochloric acid, nitric acid or trifluoroacetic acid; and/or the number of the groups of groups,
the second base includes; potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, or cesium carbonate; and/or the number of the groups of groups,
the molar ratio of the salt or amine to the third acid is 1 (5-7.5); and/or the number of the groups of groups,
the molar ratio of the salt or amine to the first aldehyde is 1 (2-3); and/or the number of the groups of groups,
the third acid comprises; formic acid, acetic acid or oxalic acid; and/or the number of the groups of groups,
the first aldehyde comprises; formaldehyde, acetaldehyde, 1-propanal, or 2-propanal; and/or the number of the groups of groups,
the molar ratio of the first catalyst to the salt or the amine is 1 (0.3-1); and/or the number of the groups of groups,
the first catalyst comprises zinc or a molecular sieve.
The invention also discloses a quaternized poly (4-aryl) piperidine polymer, which has a structure shown in the following formula (Q):
wherein Ar, R is 1 Is the same as the defined features in the poly (4-aryl) piperidine polymer;
the R is 5 Comprising a group having a quaternized structure;
preferably, said R 5 An alkyl chain comprising a quaternized structure;
preferably, said R 5 Comprising C1-C10 alkyl chains of quaternized structure.
Also disclosed is a method for preparing the quaternized poly (4-aryl) piperidine polymer, comprising the steps of adding the poly (4-aryl) piperidine polymer to a third solvent and adding a second catalyst and a haloalkane of the corresponding structure to perform a quaternization reaction, and adding a reaction solution to a fourth solvent to mix and collect a precipitate, depending on the structure of the quaternized poly (4-aryl) piperidine polymer selected.
Specifically, the preparation method of the quaternized poly (4-aryl) piperidine polymer comprises the following steps:
the solid to liquid ratio of the poly (4-aryl) polymer and the haloalkane is 1g: (1-3) mL; and/or the number of the groups of groups,
the mass ratio of the poly (4-aryl) piperidine polymer to the second catalyst is (2-3): 1, a step of; and/or the number of the groups of groups,
The second catalyst comprises K 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the solid-to-liquid ratio of the poly (4-aryl) polymer and the third solvent is 1g: (10-20) mL; and/or the number of the groups of groups,
the third solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the fourth solvent comprises at least one of ethyl acetate, methanol, ethanol, acetone or diethyl ether; and/or the number of the groups of groups,
the volume ratio of the third solvent to the fourth solvent is 1: (6-10); and/or the number of the groups of groups,
the temperature of the quaternization reaction is 40-60 ℃; and/or the number of the groups of groups,
the method further comprises a step of drying the precipitate, preferably the drying step comprises a step of vacuum drying at 60-80 ℃.
The invention also discloses a high-stability anion exchange membrane, which is an OH-type anion exchange membrane and has a structure shown in the following formula (T):
wherein Ar, R is 1 Is the same as the defined features in the poly (4-aryl) piperidine polymer;
the anion exchange membrane is prepared from a starting material comprising the poly (4-aryl) piperidine polymer and/or the quaternized poly (4-aryl) piperidine polymer.
The invention also discloses a method for preparing the high-stability anion exchange membrane, which comprises the following steps:
(1) Adding a fifth solvent into the quaternized poly (4-aryl) piperidine polymer, mixing, and casting on the surface of a substrate to obtain a polymer film;
(2) And (3) immersing the polymer membrane in a second alkali solution to obtain the OH-type anion exchange membrane.
Specifically, the preparation method of the high-stability anion exchange membrane comprises the following steps:
the solid to liquid ratio of the quaternized poly (4-aryl) piperidine polymer to the fifth solvent is 1g: (10-100) mL; and/or the number of the groups of groups,
the fifth solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the thickness of the polymer film is 20-60 mu m; and/or the number of the groups of groups,
the second alkaline solution comprises NaOH and/or KOH solution, and the preferable concentration is 0.5-2.0M; and/or the number of the groups of groups,
the temperature of the dipping step is 25-80 ℃ and the dipping time is 8-12h; and/or the number of the groups of groups,
the method further comprises the step of placing the anion exchange membrane in deionized water which is filled with a protective atmosphere for preservation.
In particular, the process for preparing a highly stable anion exchange membrane further comprises the step of preparing the desired quaternized poly (4-aryl) piperidine polymer from the poly (4-aryl) piperidine polymer according to the process.
The invention also discloses the application of the high-stability anion exchange membrane in preparing an alkaline water electrolysis tank and/or an alkaline fuel cell.
The invention also discloses an alkaline water electrolysis tank, an alkaline fuel cell and/or an alkaline fuel cell device prepared by the high-stability anion exchange membrane.
The invention also discloses the use of the poly (4-aryl) piperidine polymer and/or the quaternized poly (4-aryl) piperidine polymer for preparing anion exchange membranes.
The invention also discloses the use of the poly (4-aryl) piperidine polymer and/or the quaternized poly (4-aryl) piperidine polymer for preparing a catalytic layer coated anion membrane or gas diffusion electrode.
According to the poly (4-aryl) piperidine polymer, a polycondensation reaction is carried out by using an electron-rich linear benzene ring monomer and an N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine monomer structure, so that a skeleton structure of an all-carbon main chain is obtained, meanwhile, the main chain is not directly connected with a piperidine ring, the ion loss in the polymer is obviously reduced, and the chemical structure stability of AEM is further improved.
The poly (4-aryl) piperidine polymer of the invention further incorporates a hydrophobic structural unit R 1 The copolymer of poly (4-aryl) piperidine is obtained, and the copolymer has lower water absorption and swelling rate by copolymerization with a hydrophobic unit, so that the mechanical stability and the conductivity of AEM can be further improved, the IEC of the polymer is regulated, and the water absorption of an anion exchange membrane is changed <30%) and the swelling ratio<10 percent) improves the mechanical strength and mechanical property of the polymer, and can be used for preparing anion exchange membranes with high stability.
The invention also provides a N-methyl-4-trifluoro alkyl ketone/aryl ethyl ketone piperidine monomer structure, wherein the monomer structure connects a polymerizable trifluoro acetyl group to a fourth position of an N-methyl piperidine ring through alkyl or aryl, so that the piperidine ring is suspended outside an aryl main chain in the polymer, the distortion of the piperidine ring structure is reduced, and the anion transmission rate and the chemical stability are further improved, so that the poly (4-aryl) piperidine polymer is prepared.
The anion exchange membrane of the invention forms a quaternized poly (4-aryl) piperidine polymer based on the poly (4-aryl) piperidine polymer, and then forms an OH-type anion exchange membrane through alkalization. The anion exchange membrane has ultrahigh chemical stability, structural stability, excellent conductivity and ion conductivity, and the ion loss rate is less than 5% after being soaked in a 1M KOH solution at 80 ℃ for more than 1000 hours, so that the stability of the anion exchange membrane is greatly improved. The anion exchange membrane has excellent performance in AEM-WE, AEMFCs and other applications.
The poly (4-aryl) piperidine polymer of the invention can be used as ionomer to be prepared into catalyst ink together with catalyst, alcohol and water due to the excellent hydroxyl ion conductivity, chemical stability, mechanical property and solubility, can be used for preparing catalyst layer coated anion membrane or gas diffusion electrode, and is applied to water electrolysis, fuel cells and CO 2 In the fields of reduction and the like,further improving the stability and durability of the operation of the device.
The poly (4-aryl) piperidine polymer provided by the invention has high-stability functional cationic groups, so that the poly (4-aryl) piperidine polymer can be used for preparing an anion exchange membrane with high stability. In the anion exchange membrane with the structure, the piperidine ring is suspended outside a rigid aryl main chain, so that the anion transmission rate is improved, and the chemical stability of the anion exchange membrane is enhanced; in the anion exchange membrane with the structure, the water absorption and the swelling rate of the polymer are regulated and controlled by adding the copolymerized hydrophobic monomer, so that the mechanical strength of the polymer is improved; and the polymer has very excellent performance by being applied to alkaline electrolyzed water and fuel cells, and has very important significance for realizing industrial application of AEM electrolyzed water.
The anion exchange membrane provided by the invention has the advantages of higher water absorption and high swelling rate in the practical application process, and greatly influences the long-time stability and efficiency of an electrochemical device, aiming at the defects of AEM applied to AEM-WE and AEM-FCs in the prior art, namely the fracture of an aryl skeleton and the degradation of quaternary ammonium salt. The anion exchange membrane provides valuable information for future AEM research and development by improving the conductivity and chemical stability of the ionomer and the anion exchange membrane so as to promote the development and large-scale commercialization of AEM-WE and AEM-FCs.
The anion exchange membrane provided by the invention directly carries out super acidic polymerization on the polymer monomer by a one-pot method, simplifies the synthesis steps of the membrane, has simple preparation process, and can be matched with mass production of the membrane.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 shows the hydrogen nuclear magnetic resonance spectrum of the N-methyl-4-trifluoroacetyl piperidine monomer structure of example 1 1 H-NMR)；
FIG. 2 shows nuclear magnetic resonance fluorine spectrum of N-methyl-4-trifluoroacetyl piperidine monomer structure of example 1 19 F-NMR)；
FIG. 3 shows the nuclear magnetic resonance hydrogen spectrum of the monomer structure of 4- (N-methylpiperidin-4-yl) methyltrifluoroacetophenone of example 3 1 H-NMR)；
FIG. 4 shows nuclear magnetic resonance fluorine spectrum of 4- (N-methylpiperidin-4-yl) methyltrifluoroacetophenone monomer structure of example 3 19 F-NMR)；
FIG. 5 shows the hydrogen nuclear magnetic resonance spectrum of the monomer structure of 4- (3- (N-methylpiperidin-4-yl) propyl) trifluoroacetophenone of example 4 1 H-NMR)；
FIG. 6 shows nuclear magnetic resonance fluorine spectrum of 4- (3- (N-methylpiperidin-4-yl) propyl) trifluoroacetophenone monomer structure of example 4 19 F-NMR)；
FIG. 7 is a graph showing the water absorption and swelling ratio of the anion exchange membrane of experimental example 9;
FIG. 8 is the composition I in example 5 - Presentation of the form of anion exchange membrane;
FIG. 9 is the sample I in example 5 - Form anion exchange membrane nuclear magnetic resonance hydrogen spectrum 1 H-NMR)；
FIG. 10 is the sample I in example 5 - Anion exchange membrane nuclear magnetic resonance fluorine spectrum 19 F-NMR)；
FIG. 11 is the ionic conductivity of the anion exchange membrane and QPAP membrane prepared in example 5 at room temperature;
FIG. 12 is a LSV graph of the anion exchange membrane prepared in example 5 at various temperatures (25, 40, 60, 80 ℃) in an alkaline cell;
FIG. 13 is a graph showing EIS curves of the anion exchange membrane prepared in Experimental example 5 at different temperatures (25, 40, 60, 80 ℃) in an alkaline electrolytic cell;
fig. 14 is a polarization curve of an anion exchange membrane cell discharge of the anion exchange membrane assembly in experimental example 5.
Detailed Description
In the following examples of the invention, the (4-aryl) piperidine monomer, the poly (4-aryl) piperidine polymer, the quaternized poly (4-aryl) piperidine polymer and OH - The anion exchange membranes have structures represented by the following formulas (M), (P), (Q), and (T):
the (4-aryl) piperidine monomer, poly (4-aryl) piperidine polymer, quaternized poly (4-aryl) piperidine polymer and OH - In the structure of the type anion exchange membrane, a=0 or 1, and x is an integer of 0 to 10.
The (4-aryl) piperidine monomer, poly (4-aryl) piperidine polymer, quaternized poly (4-aryl) piperidine polymer and OH - Ar and R in the structure of anion exchange membrane 1 Representing the same group.
The poly (4-aryl) piperidine polymers described above, quaternized poly (4-aryl) piperidine polymers and OH - In the structure of the anion exchange membrane, ar is phenyl structural monomer with a linear structure, and substances known in the art are selected to form the required structural characteristics. In the following examples of the present invention, as an exemplary scheme, examples such as biphenyl, p-terphenyl, tetrabiphenyl, m-terphenyl, diphenylethane, trans-1, 2-stilbene, cis-1, 2-stilbene, dialkyl-substituted fluorenes (R 2 Are alkyl chains C1-C10), N-R 2 Carbazole (R) 2 Is alkyl chain C1-C10), dibenzo-18-crown-6, 1' -binaphthyl, diphenyl ether, xanthene, 6' -dimethoxy-3, 3' -tetramethyl-1, 1' -spiroindane, 9' -dialkyl substituted-2, 7-diphenylfluorene (R) 2 The monomer structure of alkyl chain C1-C10) is used as raw material for reaction.
The poly (4-aryl) piperidine polymers described above, quaternized poly (4-aryl) piperidine polymers and OH - In the structure of the anion exchange membrane, the R is 1 For hydrophobic co-units, materials known in the art may be selected to form the desired structural features. In the following examples of the invention, the hydrophobic co-units are formed by the reaction of corresponding ketone monomers. As an exemplary scheme, there may be selected, for example, trifluoroacetophenone, trifluoroacetyl compound (R 3 Alkyl), 2, 3-butanedione, N-R 4 Isatin (R) 4 Is hydrogen atom, alkyl chain and aryl group), and pentafluorobenzaldehyde is used as ketone monomer to form R through reaction 1 The hydrophobic co-polymer unit structure shown.
In the structure of the poly (4-aryl) piperidine polymer, the quaternized poly (4-aryl) piperidine polymer and the OH-type anion exchange membrane, the linear structure polymerization unit comprises:
y n molar ratio,%, of polymerized units containing the N-methyl-4-trifluoroalkyl ketone/trifluoroaryl ethyl ketone piperidine structure in the polymer;
y m To contain said hydrophobic comonomer R 1 Molar ratio,%;
wherein y is n 60% -100%; y is m 0% -40% and y n +y m ＝100％。
In the following examples, the synthesis method of the poly (4-aryl) piperidine polymer can be realized by regulating and controlling the linear structure phenyl monomer Ar, N-methyl-4-trifluoro alkyl ketone/trifluoro aryl ethyl ketone piperidine structure and the hydrophobic copolymerization unit R 1 The proportion of monomers is subjected to polycondensation reaction under the catalysis of trifluoromethanesulfonic acid to synthesize a series of homopolymers of poly (4-aryl) piperidine and poly (4-aryl) piperidine copolymers of different IEC, and the polymers are prepared into polymer films which are used in anion exchange membrane alkaline water electrolysis devices and anion exchange membrane fuel cell devices.
In the following examples, the process for synthesizing the quaternized poly (4-aryl) piperidine polymer is based on the poly (4-aryl) piperidine polymer by adding K 2 CO 3 And the corresponding structure of the halogenated alkane are subjected to quaternization reaction to prepare the modified halogenated alkane.
In the following examples, the method for synthesizing the high-stability anion exchange membrane, namely the OH-type anion exchange membrane, is to form a membrane by using a solvent evaporation mode on the basis of the quaternized poly (4-aryl) piperidine polymer, and then to dip the formed polymer membrane in an alkaline solvent.
The invention is further illustrated by the following specific experimental procedures. The following examples are intended to illustrate the invention without further limiting it.
Example 1
The embodiment provides a synthesis method of an N-methyl-4-trifluoroacetyl piperidine monomer structure, which is used for improving the alkaline stability of AEM, and the specific structure is shown as follows.
The monomer structure of the embodiment is prepared by the following method:
(1) In a 500mL three-necked flask, commercially available 4-piperidinecarboxylic acid (12.92 g,100 mmol) and toluene (50 mL) were added, stirred with a magnetic stirrer at room temperature under nitrogen atmosphere for 5min, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (78 mL,560 mmol) was added to the three-necked flask, pyridine (64.5 mL,800 mmol) was then added dropwise to the mixed solution, after stirring with an ice-water bath for 15min, the apparatus was returned to room temperature, and finally reacted at 50℃for 48h. After the reaction was completed, the reaction apparatus was cooled to room temperature and transferred to an ice-water bath, 200mL of water was added to the mixed solution, and stirred at 45 ℃ for 2 hours. And (3) post-reaction treatment: cooling the reaction system to room temperature, extracting with ethyl acetate (3X 100 mL), separating the solution, adding water (150 mL) into the organic phase for back extraction, separating the solution, collecting the organic phase, adding saturated sodium carbonate solution (150 mL) into the organic phase, separating the solution, collecting the organic phase, drying saturated sodium chloride aqueous solution (150 mL) into the organic phase, separating the solution, collecting the organic phase, finally drying the organic phase with anhydrous sodium sulfate, and spin-drying the dried organic phase with a vacuum rotary evaporator to obtain black thick liquid;
(2) The black thick liquid is simply purified by using a quick silica gel short column, and the developing agent is prepared from petroleum ether: ethyl acetate = 100:0 to 50:50, removing a large amount of low-polarity byproducts and high-polarity salts, and spin-drying the obtained crude product by a vacuum rotary evaporator to obtain yellow oily matter which is directly used in the next step. Reflux is carried out overnight at 100 ℃ under concentrated hydrochloric acid for complete deprotection, a solution system after the reaction is dried by a vacuum rotary evaporator to obtain black solid, and then the black solid is recrystallized in acetonitrile to obtain white crystal 4-trifluoroacetyl piperidine hydrochloride with higher purity, wherein the product quality is 14.10g, and the yield is 65%;
(3) In a 100mL two-necked flask, 4-trifluoroacetyl piperidine hydrochloride (10.88 g,50 mmol), formic acid (9.4 mL,250 mmol) and 36wt% formaldehyde solution (9.0 mL,110 mmol) were added to the flask under ice-water bath, and refluxed at 100℃for 16 hours. Post-treatment: after the reaction was completed, the solution was cooled to room temperature, then 2M hydrochloric acid solution (25 mL) was added, spin-dried using a vacuum rotary evaporator, then water (25 mL) was added, and washed with 20% sodium hydroxide solution, finally ethyl acetate was added for extraction, and the organic phase was collected and spin-dried, and the obtained mixture was purified by column chromatography.
Example 2
The embodiment provides a synthetic method of an N-methyl-4-trifluoroacetone-based piperidine monomer structure, which is used for improving the alkaline stability of AEM, and the specific structure is shown as follows.
The monomer structure of the embodiment is prepared by the following method:
(1) Commercial 2- (piperidin-4-yl) acetate (17.97 g,100 mmol) was pretreated to remove hydrochloric acid, followed by extraction and concentration. In a 500mL three-necked flask, treated 2- (piperidin-4-yl) acetic acid and toluene (50 mL) were added, stirred with a magnetic stirrer at room temperature under nitrogen atmosphere for 5min, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (78 mL,560 mmol) was added to the three-necked flask, pyridine (64.5 mL,800 mmol) was then added dropwise to the mixed solution, after stirring in the ice-water bath for 15min, the apparatus was returned to room temperature, and finally reacted at 50℃for 48h. After the reaction was completed, the reaction apparatus was cooled to room temperature and transferred to an ice-water bath, 200mL of water was added to the mixed solution, and stirred at 45 ℃ for 2 hours. And (3) post-reaction treatment: cooling the reaction system to room temperature, extracting with ethyl acetate (3X 100 mL), separating the solution, adding water (150 mL) into the organic phase for back extraction, separating the solution, collecting the organic phase, adding saturated sodium carbonate solution (150 mL) into the organic phase, separating the solution, collecting the organic phase, drying saturated sodium chloride aqueous solution (150 mL) into the organic phase, separating the solution, collecting the organic phase, finally drying the organic phase with anhydrous sodium sulfate, and spin-drying the dried organic phase with a vacuum rotary evaporator to obtain black thick liquid;
(2) The black thick liquid is simply purified by using a quick silica gel short column, and the developing agent is prepared from petroleum ether: ethyl acetate = 100:0 to 55:45, removing a large amount of low-polarity byproducts and high-polarity salts, and spin-drying the obtained crude product by a vacuum rotary evaporator to obtain yellow oily matter which is directly used in the next step. Reflux is carried out overnight at 100 ℃ under concentrated hydrochloric acid for complete deprotection, a solution system after the reaction is dried by a vacuum rotary evaporator to obtain black solid, and then the black solid is recrystallized in acetonitrile to obtain 3- (N-methylpiperidine-4-yl) trifluoro-2-propanone hydrochloride crystal with higher purity and off-white color, wherein the product quality is 9.83g, and the product yield is 40%;
(3) In a 100mL two-necked flask, 3- (N-methylpiperidin-4-yl) trifluoro-2-propanone hydrochloride crystal (9.83 g,40 mmol), formic acid (7.5 mL,200 mmol) and 36wt% formaldehyde solution (7.2 mL,88 mmol) were added to the flask under ice-water bath conditions, and refluxed at 100℃for 16h. Post-treatment: after the reaction was completed, the solution was cooled to room temperature, then 2M hydrochloric acid solution (25 mL) was added, spin-dried using a vacuum rotary evaporator, then water (25 mL) was added, and washed with 20% sodium hydroxide solution, finally ethyl acetate was added for extraction, and the organic phase was collected and spin-dried, and the obtained mixture was purified by column chromatography.
Example 3
The embodiment provides a synthetic method of a 4- (N-methylpiperidin-4-yl) methyltrifluoroacetophenone monomer structure, which is used for improving the alkaline stability of AEM, and the specific structure is shown as follows.
The monomer structure of the embodiment is prepared by the following method:
(1) In a 500mL three-necked flask, 4-benzylpiperidine (17.53 g,100 mmol) and methylene chloride (150 mL) which were commercially available were added, stirred with a magnetic stirrer at room temperature under a nitrogen atmosphere for 5 minutes, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (15.3 mL,110 mmol) was added to the three-necked flask, then N, N-diisopropylethylamine (18.5 mL,110 mmol) was added dropwise to the mixed solution, after stirring with an ice-water bath for 15 minutes, the apparatus was returned to room temperature, and the reaction was carried out at room temperature for 12 hours. And (3) post-reaction treatment: the reaction system is cooled to room temperature, water (100 mL) is added into the reaction system, the organic phase is taken, 1M hydrochloric acid solution (100 mL) is added into the organic phase, the organic phase is taken, saturated sodium bicarbonate solution (100 mL) is dried in the organic phase, the organic phase is taken, finally, anhydrous sodium sulfate is used for drying the organic phase, the dried organic phase is spin-dried by a vacuum rotary evaporator, the spin-dried liquid is simply purified by a quick silica gel short column, and the developing agent is petroleum ether: ethyl acetate = 100:0 to 75:25, obtaining a crude product;
(2) In a 500mL three-necked flask, aluminum trichloride (30 g,225 mmol) and methylene chloride (100 mL) were added first, stirred with a magnetic stirrer at room temperature under nitrogen atmosphere for 5min, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (19.5 mL,140 mmol) was added to the three-necked flask, after stirring uniformly, the crude product of the previous step was dissolved in methylene chloride (50 mL), added dropwise to the reaction system, then transferred to room temperature conditions, and reacted at room temperature for 2h. And (3) post-reaction treatment: the reaction system was cooled to room temperature, the reaction system was poured into ice cubes, the organic phase was taken out, 1M hydrochloric acid solution (100 mL) was added to the organic phase, the organic phase was taken out, the aqueous phase was then washed with dichloromethane (2×20 mL), the organic phase was taken out, all the organic phases were combined, saturated sodium chloride solution (100 mL) was added to the organic phase for drying, the organic phase was taken out, finally the organic phase was dried with anhydrous sodium sulfate, and the dried organic phase was spin-dried with a vacuum rotary evaporator. Purifying the liquid after spin drying by using a column chromatography method, wherein the developing agent is prepared from petroleum ether: ethyl acetate = 100:0 to 80:20, obtaining pale yellow liquid 4- (1- (N-trifluoro acetyl piperidine-4-yl) methyl) trifluoro acetophenone, the product quality is 25.69g, and the yield is 70%;
(3) In a 250mL double-necked flask, the above-mentioned product (12.85 g,50 mmol) and concentrated hydrochloric acid were added, and the mixture was refluxed overnight at 100℃to completely deprotect, and the solution system after the completion of the reaction was dried by spin-drying using a vacuum rotary evaporator. The hydrochloride salt, formic acid (9.4 mL,250 mmol) and 36wt% formaldehyde solution (9.0 mL,110 mmol) were then added to the flask in a 250mL two-necked flask under ice-water bath and refluxed at 100℃for 16h. Post-treatment: after the reaction was completed, the solution was cooled to room temperature, then 2M hydrochloric acid solution (25 mL) was added, spin-dried using a vacuum rotary evaporator, then water (25 mL) was added, and washed with 20% sodium hydroxide solution, finally ethyl acetate was added for extraction, and the organic phase was collected and spin-dried, and the obtained mixture was purified by column chromatography.
Example 4
The embodiment provides a synthetic method of a 4- (3- (N-methylpiperidine-4-yl) propyl) trifluoroacetophenone monomer structure, which is used for improving the alkaline stability of AEM, and the specific structure is shown as follows.
The monomer structure of the embodiment is prepared by the following method:
(1) In a 500mL three-necked flask, commercially available 4- (3-phenylpropyl) piperidine (20.33 g,100 mmol) and methylene chloride (150 mL) were added, stirred with a magnetic stirrer at room temperature under nitrogen atmosphere for 5min, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (15.3 mL,110 mmol) was added to the three-necked flask, then N, N-diisopropylethylamine (18.5 mL,110 mmol) was added dropwise to the mixed solution, after stirring with an ice-water bath for 15min, the apparatus was returned to room temperature, and reacted at room temperature for 12h. And (3) post-reaction treatment: the reaction system is cooled to room temperature, water (100 mL) is added into the reaction system, the organic phase is taken, 1M hydrochloric acid solution (100 mL) is added into the organic phase, the organic phase is taken, saturated sodium bicarbonate solution (100 mL) is dried in the organic phase, the organic phase is taken, finally, anhydrous sodium sulfate is used for drying the organic phase, the dried organic phase is spin-dried by a vacuum rotary evaporator, the spin-dried liquid is simply purified by a quick silica gel short column, and the developing agent is petroleum ether: ethyl acetate = 100:0 to 80:20, obtaining a crude product;
(2) In a 500mL three-necked flask, aluminum trichloride (30 g,225 mmol) and methylene chloride (100 mL) were added first, stirred with a magnetic stirrer at room temperature under nitrogen atmosphere for 5min, then the three-necked flask was transferred to an ice-water bath, trifluoroacetic anhydride (19.5 mL,140 mmol) was added to the three-necked flask, after stirring uniformly, the crude product of the previous step was dissolved in methylene chloride (50 mL), added dropwise to the reaction system, then transferred to room temperature conditions, and reacted at room temperature for 2h. And (3) post-reaction treatment: the reaction system was cooled to room temperature, the reaction system was poured into ice cubes, the organic phase was taken out, 1M hydrochloric acid solution (100 mL) was added to the organic phase, the organic phase was taken out, the aqueous phase was then washed with dichloromethane (2×20 mL), the organic phase was taken out, all the organic phases were combined, saturated sodium chloride solution (100 mL) was added to the organic phase for drying, the organic phase was taken out, finally the organic phase was dried with anhydrous sodium sulfate, and the dried organic phase was spin-dried with a vacuum rotary evaporator. Purifying the liquid after spin drying by using a column chromatography method, wherein the developing agent is prepared from petroleum ether: ethyl acetate = 100:0 to 85:15, obtaining pale yellow liquid 4- (3- (N-trifluoro acetyl piperidine-4-yl) propyl) trifluoro acetophenone, the product quality is 31.63g, and the yield is 80%;
(3) In a 250mL double-necked flask, the above-mentioned product (19.77 g,50 mmol) and concentrated hydrochloric acid were added, and the mixture was refluxed overnight at 100℃to completely deprotect, and the solution system after the completion of the reaction was dried by spin-drying using a vacuum rotary evaporator. The hydrochloride salt, formic acid (9.4 mL,250 mmol) and 36wt% formaldehyde solution (9.0 mL,110 mmol) were then added to the flask in a 250mL two-necked flask under ice-water bath and refluxed at 100℃for 16h. Post-treatment: after the reaction was completed, the solution was cooled to room temperature, then 2M hydrochloric acid solution (25 mL) was added, spin-dried using a vacuum rotary evaporator, then water (25 mL) was added, and washed with 20% sodium hydroxide solution, finally ethyl acetate was added for extraction, and the organic phase was collected and spin-dried, and the obtained mixture was purified by column chromatography.
Example 5
This example provides an OH-type anion exchange membrane of a polyaryltrifluoroacetyl dimethylpiperidine homopolymer, the specific structure of which is shown below.
The anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol) and N-methyl-4-trifluoroacetyl piperidine (1.0735 g,5.5 mmol) are added into methylene dichloride (5 mL), a magnetic stirrer is used for stirring for 10min under the ice-water bath and air atmosphere to obtain a white mixed solution, TFSA (5.0 mL,56.50 mmol) is then dropwise added into the white mixed solution, stirring is carried out after the dropwise addition is finished for 40h, the color of the solution is changed from red to deep blue during the reaction, and the obtained viscous solution is poured into 200ml+200mL of water and methanol mixed solution to precipitate a light yellow polymer;
(2) The pale yellow polymer was crushed, and the crushed pieces were collected by filtration, using 1M K 2 CO 3 Stirring and washing the solution at room temperature for 12 hours to neutralize acid remained in the reaction, washing the solution with deionized water for three times, and drying the solution in a vacuum oven at 80 ℃ for 12 hours to obtain a polyaryltrifluoroacetyl methylpiperidine homopolymer;
(3) In a flask, the resulting polyaryltrifluoroacetyl methylpiperidine homopolymer (2.0 g) was dissolved in DMSO (40 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60 ℃ and stirring for 6 hours, adding the obtained viscous solution into 200mL of diethyl ether, filtering yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a quaternized polyaryltrifluoroacetyl dimethylpiperidine homopolymer;
(4) Quaternized polyaryltrifluoroacetyl dimethylpiperidine homopolymer (0.4 g) was dissolved in DMSO (20 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried for 8 hours on a solvent volatilization heating station at 120 ℃ to completely remove residual solvent to give a 40 μm thick I-type polymer film;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, ion exchanging at 60deg.C for 12 hr to obtain OH-type film, and washing with deionized water for 3 times to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, an OH-type polyaryltrifluoroacetyl dimethylpiperidine homopolymer was finally obtained. The anion exchange membrane prepared in this example (36. Pi. Cm in area) 2 Film) which is uniform in thickness and transparent in texture.
Example 6
This example provides an OH-type anion exchange membrane of a polyaryltrifluoroacetonyl piperidine homopolymer, the specific structure of which is shown below.
The anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol) and 3- (N-methylpiperidin-4-yl) trifluoro-2-propanone (1.2553 g,6.0 mmol) were added to dichloromethane (5 mL), stirred with a magnetic stirrer under ice-water bath and air atmosphere for 10min to obtain a white mixed solution, TFSA (5.0 mL,56.50 mmol) was then added dropwise to the above white mixed solution, stirred and reacted for 48h after the dropwise addition, during the reaction, the color of the solution turned from red to dark blue, and the obtained viscous solution was poured into 200ml+200mL of water and methanol mixed solution to precipitate a pale yellow polymer;
(2) The pale yellow polymer was crushed, and the crushed pieces were collected by filtration, using 1M K 2 CO 3 Stirring and washing the solution at room temperature for 12 hours to neutralize acid remained in the reaction, washing the solution with deionized water for three times, and drying the solution in a vacuum oven at 80 ℃ for 12 hours to obtain a polyaryltrifluoroacetone-based methylpiperidine homopolymer;
(3) At the position ofIn a flask, the resulting polyaryltrifluoroacetonylmethylpiperidine homopolymer (2.0 g) was dissolved in DMSO (40 mL), stirred at room temperature for 30min, and then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60 ℃ and stirring for 6 hours, adding the obtained viscous solution into 200mL of diethyl ether, filtering yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a quaternized polyaryltrifluoroacetonyl dimethylpiperidine homopolymer;
(4) The quaternized polyaryltrifluoroacetonyl dimethylpiperidine homopolymer (0.4 g) was dissolved in DMSO (20 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried for 8h on a solvent evaporation heated station at 120℃to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, OH is finally obtained - A polyaryltrifluoroacetonyldimethylpiperidine homopolymer of the type.
Example 7
This example provides an OH group of a polyaryltrifluoroacetyl benzyl dimethyl piperidine homopolymer - The specific structure of the anion exchange membrane is shown below.
The anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol) and 4- (4- (N-methylpiperidin-4-yl) methyl) trifluoroacetophenone (1.5682 g,5.5 mmol) were added to methylene chloride (5 mL), stirred with a magnetic stirrer under an ice-water bath and air atmosphere for 10min to obtain a white mixed solution, TFSA (5.0 mL,56.50 mmol) was then added dropwise to the above white mixed solution, and stirred for 48h after the dropwise addition, during the reaction, the color of the solution was changed from red to deep blue, and the obtained viscous solution was poured into 200ml+200mL of a mixed solution of water and methanol to precipitate a pale yellow polymer;
(2) The pale yellow polymer was crushed, and the crushed pieces were collected by filtration, using 1M K 2 CO 3 Stirring and washing the solution at room temperature for 12 hours to neutralize acid remained in the reaction, washing the solution with deionized water for three times, and drying the solution in a vacuum oven at 80 ℃ for 12 hours to obtain a polyaryltrifluoroacetyl benzyl methyl piperidine homopolymer;
(3) In a flask, the resulting polyaryltrifluoroacetyl benzyl methylpiperidine homopolymer (2.0 g) was dissolved in DMSO (40 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60 ℃ and stirring for 6 hours, adding the obtained viscous solution into 200mL of diethyl ether, filtering yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a quaternized polyaryltrifluoroacetyl benzyl dimethylpiperidine homopolymer;
(4) The quaternized polyaryltrifluoroacetyl benzyl dimethyl piperidine homopolymer (0.4 g) was dissolved in DMSO (20 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried in a solvent evaporation heated station at 120deg.C for 8h to remove residual solvent completely to give a 40 μm thick I - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, OH is finally obtained - A polyarylene trifluoroacetyl benzyl dimethyl piperidine homopolymer of type.
Example 8
This example provides an OH group of a polyaryltrifluoroacetyl phenyl propyl dimethylpiperidine homopolymer - The specific structure of the anion exchange membrane is shown below.
The anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol) and 4- (3- (N-methylpiperidin-4-yl) propyl) trifluoroacetophenone (2.0368 g,6.5 mmol) were added to methylene chloride (5 mL), stirred with a magnetic stirrer under an ice-water bath and air atmosphere for 10min to obtain a white mixed solution, TFSA (5.0 mL,56.50 mmol) was then added dropwise to the above white mixed solution, and stirred for 48h after the dropwise addition, during the reaction, the color of the solution was changed from red to deep blue, and the obtained viscous solution was poured into 200ml+200mL of a mixed solution of water and methanol to precipitate a pale yellow polymer;
(2) The pale yellow polymer was crushed, and the crushed pieces were collected by filtration, using 1M K 2 CO 3 Stirring and washing the solution at room temperature for 12 hours to neutralize acid remained in the reaction, washing the solution with deionized water for three times, and drying the solution in a vacuum oven at 80 ℃ for 12 hours to obtain a polyaryltrifluoroacetyl phenyl propyl methyl piperidine homopolymer;
(3) In a flask, the resulting polyaryltrifluoroacetyl phenylpropanoid methylpiperidine homopolymer (2.0 g) was dissolved in DMSO (40 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.637 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60 ℃ and stirring for 6 hours, adding the obtained viscous solution into 200mL of diethyl ether, filtering yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a quaternized polyaryltrifluoroacetyl phenylpropanoid dimethyl piperidine homopolymer;
(4) Quaternized polyaryltrifluoroacetyl phenylpropanoid dimethylpiperidine homopolymer (0.4 g) was dissolved in DMSO (20 mL) and the polymer solution was passed through 0.45Filtering with Polytetrafluoroethylene (PTFE) filter, casting on a flat clean glass plate, oven drying at 120deg.C for 8 hr, and completely removing residual solvent to obtain a 40 μm thick I - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, OH is finally obtained - A polyaryltrifluoroacetyl phenyl propyl dimethylpiperidine homopolymer.
Example 9
This example provides a low IEC poly (aryl trifluoroacetyl methyl piperidine) copolymer OH - The specific structure of the anion exchange membrane is shown below.
The anion exchange membrane described in this example is prepared by the following method:
(1) In a 100mL single-neck flask, p-terphenyl (1.1545 g,5.0 mmol), N-methyl-4-trifluoroacetyl piperidine (0.9125 g,4.675 mmol) and trifluoroacetophenone (0.1436 g, 0.8235 mmol) are added into dichloromethane (5 mL), and stirred under an ice-water bath and air atmosphere by a magnetic stirrer for 10min to obtain a light yellow mixed solution, TFSA (5.0 mL,56.50 mmol) is then added dropwise into the white mixed solution, and stirred and reacted for 72h after the dropwise addition, wherein the color of the solution is changed from light yellow to red finally to dark blue in the reaction process, and the obtained viscous solution is poured into a 200mL+200mL mixed solution of water and methanol to precipitate a yellow polymer;
(2) The yellow polymer was crushed and the fragments were collected by filtration using 1M K 2 CO 3 Is washed with stirring at room temperature for 12 hours to neutralize the acid remaining after the reaction, is then washed with deionized water three times, is heated to 80 DEG CDrying for 12h in a vacuum oven to give a poly (aryl trifluoroacetyl methylpiperidine) copolymer (iec=2.40 mmol/g);
(3) In a flask, a polyaryltrifluoroacetyl methylpiperidine copolymer (3.0 g) was dissolved in DMSO (50 mL), stirred at room temperature for 30min, then K was added 2 CO 3 (0.687 g) and methyl iodide (5.0 mL), stirring at room temperature in the dark for 12 hours, then heating to 60 ℃ and stirring for 6 hours, adding 200mL diethyl ether into the obtained viscous solution, filtering yellow precipitate, washing 3 times with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain the quaternized polyaryltrifluoroacetyl dimethylpiperidine copolymer;
(4) The quaternized polyaryltrifluoroacetyl dimethylpiperidine copolymer (0.4 g) was dissolved in DMSO (15 mL), the polymer solution was filtered through a 0.45 μm Polytetrafluoroethylene (PTFE) filter, cast onto a flat, clean glass plate, and then dried in a solvent evaporation heated station at 120deg.C for 6 hours to give a 40 μm thick I after complete removal of residual solvent - A polymer film of the type;
(5) Will I - Stripping the polymer film from the glass plate, soaking in 1M KOH solution, and ion-exchanging at 60deg.C for 12 hr to obtain OH - The shaped film was then washed 3 times with deionized water to avoid CO 2 And carbonate formation, the membranes were immersed in deionized water purged with nitrogen for storage.
In this example, OH is finally obtained - Poly (aryl trifluoroacetyl) dimethylpiperidine copolymer of the type.
Experimental example
1. Nuclear magnetic characterization
In this example, the monomer structures prepared in examples 1, 3, and 4 were used for nuclear magnetic characterization.
This example uses 1H NMR of the reported new monomer structure as determined by Bruker 500MHz or 600MHz nuclear magnetic resonance using deuterated chloroform (CDCl) 3 0.03% TMS) or deuterated dimethyl sulfoxide (DMSO-d) 6 0.03% TMS) as deuterating reagent, the 1H spectrum of the compound was scaled with tetramethylsilane (TMS, δ=0.00 ppm) and the 13C spectrum was scaled with CDCl3 (δ=77.00 ppm) or DMSO-d6 (δ=39.50 ppm).
5-10mg of the monomer structure is dissolved in 0.5mL of deuterated chloroform and transferred to a nuclear magnetic tube for testing.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the N-methyl-4-trifluoroacetyl piperidine monomer structure of example 1.
FIG. 2 is a nuclear magnetic resonance fluorine spectrum of the N-methyl-4-trifluoroacetyl piperidine monomer structure of example 1.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the monomer structure of 4- (N-methylpiperidin-4-yl) methyltrifluoroacetophenone of example 3.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the monomer structure of 4- (N-methylpiperidin-4-yl) methyltrifluoroacetophenone of example 3.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the monomer structure of 4- (3- (N-methylpiperidin-4-yl) propyl) trifluoroacetophenone in example 4.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the monomer structure of 4- (3- (N-methylpiperidin-4-yl) propyl) trifluoroacetophenone in example 4.
2. Water absorption and swelling test
In this experimental example, OH of the low IEC polyaryltrifluoroacetyl dimethylpiperidine copolymer prepared in example 9 was taken - The resulting membranes were tested for water absorption and swelling.
Taking the OH - The anion exchange membrane after exchange is soaked in deionized water with different temperatures to reach adsorption equilibrium. After the surface water was blotted dry, the weight (Wwet) and length (Lwet) of the wet sample were measured. The films were then dried in a vacuum oven at 80 ℃ for 24 hours to measure the weight (Wdry) of each film in the dry state. WU and SR were calculated by the following formulas, and the calculation results are shown in fig. 7.
From the attached FIG. 7As can be seen, the low IEC polyarylene trifluoroacetyl piperidine copolymer prepared in example 9 has OH - The water absorption rate (80 ℃ C.) of the anion exchange membrane at different temperatures (25, 40, 50, 60, 70, 80 ℃ C.),<30%) and the swelling ratio (80 c,<10%). The membrane has lower water absorption and swelling rate, ensures mechanical properties, and meets the established standard (swelling rate is less than or equal to 10 percent) of the national 2023 anion exchange membrane water electrolysis hydrogen production electrolysis stack technology.
3. Electrode performance test
The experimental example further performs electrochemical tests on the performance of the electrode formed by the anion exchange membrane.
The anion exchange membrane prepared in example 5 and the anode catalyst NiFe catalyst and the cathode catalyst ptrac were assembled into membrane electrodes, mounted in an AEM cell and subjected to electrochemical testing at an Autolab electrochemical workstation.
In this experimental example, the anode and cathode catalysts were 1cm by 1cm in size, and the electrolyte solution of the AEM cell was 1M KOH solution.
In the AEM cell assembly process, the electrolyte solution is heated to a specific temperature (25, 40, 50, 60, 70, 80 ℃) by a heating rod, and then the heated electrolyte solution is respectively conveyed to an anode and a cathode of the AEM cell by a peristaltic pump.
Before electrochemical testing, the electrolyte solution is circulated for 20min to ensure the constant temperature of the whole testing system, then the whole electrolytic cell is subjected to scanning activation of a cyclic voltammetry Curve (CV), and after the CV curve is kept stable, the linear voltammetry scanning (LSV) test is performed.
Wherein, the voltage range of LSV test is 1.0-2.1V, the sweeping speed is 10mV/s, and the test temperature (25, 40, 60, 80 ℃).
Subsequently, the AEM cell was tested for alternating current impedance (EIS) at 1.8V at 80℃using a two electrode method, wherein the impedance was tested at a frequency in the range of 100KHz-0.1hz and an amplitude of 10mV at test temperatures (25, 40, 60, 80 ℃).
FIG. 8 is a diagram of I in this embodiment - Presentation of the form of anion exchange membrane.
FIG. 9 is a diagram of I in this embodiment - Nuclear magnetic resonance hydrogen spectrum of the form of anion exchange membrane.
FIG. 10 is a diagram showing I in the present embodiment - Nuclear magnetic resonance fluorine spectrum of the form of anion exchange membrane.
FIG. 11 shows the ionic conductivities of the anion exchange membranes and QPAP membranes prepared in example 5 at room temperature. As can be seen, the film of this example has a conductivity of 45.25mS cm at room temperature -1 Conductivity higher than that of QPAP film at the same temperature (20.60 mS cm -1 ) The anion exchange membrane of the embodiment has good application prospect.
FIG. 12 is a LSV curve based on the polymer film of example 5 at various temperatures (25, 40, 60, 80 ℃). It can be seen that at 80℃: the current density can reach 4.8A/cm under the 2V overpotential 2 。
FIG. 13 is an EIS curve based on the polymer film of example 5 at various temperatures (25, 40, 60, 80 ℃). It can be seen that the electrochemical impedance is 0.081 Ω at 80 ℃, and has higher current density and lower electrochemical impedance performance, which is superior to most anion exchange membranes in the market at present.
4. Performance test of anion exchange membrane fuel cell
The experimental example is used for testing the performance of the anion exchange membrane fuel cell prepared by the anion exchange membrane.
Preparation of a membrane electrode: the polymer of Synthesis example 9 was used as the ionomer binder for the catalytic layer, the membrane obtained in example 5 was used as the anion exchange membrane, the thickness was 50. Mu.m, platinum carbon and platinum ruthenium carbon were used as the cathode and anode catalysts, respectively, and the metal platinum loading was 1mg/cm 2 The mass ratio of the catalyst to the ionic polymer is 4:1, preparing the membrane electrode by adopting a spraying method.
Battery assembly and performance testing: sealing gaskets, graphite flow fields, gold-plated current collectors, insulating gaskets, heating end plates and the like are sequentially assembled on two sides of the membrane electrode to obtain a single cell, and the effective area of the electrode is 1cm 2 . The cathode and the anode of the battery are respectively filled with humidified oxygenAnd hydrogen (purity greater than 99%,100% humidification) at a flow rate of 500mL/min, and testing the current-voltage polarization curve of the battery at 60 ℃ after the battery is stable in operation.
Fig. 14 is a polarization curve of an anion exchange membrane cell discharge based on the anion exchange membrane assembly in example 5. It can be seen that the open circuit voltage of the cell was 1.01V and the maximum power density was 598mW/cm 2 The corresponding current density is 1200mA/cm when the maximum power density is reached 2 The voltage was 0.498V. The single cell maintains good running stability in the observation time interval of the test.
The polymer solution can be used as ionomer to be prepared into catalyst ink together with catalyst, alcohol and water for preparing an anion membrane or a gas diffusion electrode coated by a catalytic layer, so that the stability and durability of the operation of the device can be improved.
In summary, the poly (4-aryl) piperidine polymers prepared by the N-methyl-4-trifluoro alkyl/trifluoro aryl ethyl ketone piperidine monomers provided by the invention have good electrochemical performance and chemical stability, have a skeleton structure of an all-carbon main chain, and meanwhile, the main chain and a piperidine ring are not directly connected, so that the ion loss is remarkably reduced, and the chemical structural stability of AEM is further improved, so that the poly (4-aryl) piperidine polymers can be used for preparing anion exchange membranes with high stability.
In the anion exchange membrane with the structure, the water absorption and the swelling rate of the polymer are regulated and controlled by adding the copolymerized hydrophobic monomer, the mechanical strength of the polymer is improved, and the polymer has very excellent performance by being applied to alkaline electrolyzed water and fuel cells, so that the polymer has very important significance for realizing industrial application of AEM electrolyzed water.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (19)
1. A poly (4-aryl) piperidine polymer, characterized in that the polymer comprises a piperidine structure polymerized unit having a structure represented by the following formula (P1);
wherein,
a is 0 or 1;
x is an integer of 0 to 10;
ar is a phenyl structural monomer with a linear structure.
2. The poly (4-aryl) piperidine polymer according to claim 1, wherein said polymer further comprises a linear structure polymeric unit having a structure represented by the following formula (P2);
wherein,
ar is a phenyl structural monomer with a linear structure;
the R is 1 Is a hydrophobic copolymerized unit.
3. The poly (4-aryl) piperidine polymer according to claim 1 or 2, characterized in that the polymer has the structure represented by the following formula (P):
wherein,
a is 0 or 1;
x is an integer of 0 to 10;
ar is a phenyl structural monomer with a linear structure;
the R is 1 Is a hydrophobic copolymerized unit.
4. The poly (4-aryl) piperidine polymer of claim 3, wherein said poly (4-aryl) piperidine polymer comprises piperidine structural polymeric units and linear structural polymeric units; wherein,
y n mole ratio,%;
y m mole ratio,%, of polymerized units in the polymer for the linear structure;
wherein y is n 60% -100%; y is m 0% -40% and y n +y m ＝100％。
5. The poly (4-aryl) piperidine polymer according to any one of claims 1-4, wherein in Ar, the phenyl structural monomers comprise 2-4 linearly linked substituted or unsubstituted phenyl monomers;
preferably, in the phenyl structural monomers, each phenyl monomer is connected by a single bond, an unsaturated bond or forms a linear annular structure;
preferably, the Ar comprises at least one of the following structural phenyl monomers:
wherein R is 2 Are alkyl chains C1-C10.
6. The poly (4-aryl) piperidine polymer according to any one of claims 3-5, wherein R 1 Wherein the hydrophobic copolymerization unit comprises a hydrophobic monomer containing an electron withdrawing group structure;
preferably, the hydrophobic co-polymer unit comprises a substituted or unsubstituted aromatic ring hydrophobic monomer, a substituted or unsubstituted saturated aliphatic hydrophobic monomer, or a substituted or unsubstituted ketone hydrophobic monomer;
preferably, the hydrophobic co-polymer unit is selected from monomers comprising trifluoromethyl, carbonyl and/or pentafluorobenzene structures;
preferably, said R 1 At least one of the hydrophobic co-units comprising the structure:
wherein R is 3 Is alkyl; r is R 4 Is hydrogen, an alkyl chain or an aryl group;
preferably, the hydrophobic co-units are formed by the reaction of corresponding ketone monomers.
7. A process for preparing a poly (4-aryl) piperidine polymer according to any one of claims 3-6, comprising taking the phenyl structural monomer Ar, (4-aryl) piperidine monomer, and the hydrophobic co-unit R in a linear structure according to the selected structure of the poly (4-aryl) piperidine polymer 1 Adding the corresponding ketone monomer into a first solvent for mixing, carrying out polymerization reaction in the presence of a first catalyst, adding a reaction solution into a second solvent for mixing, and collecting a precipitated polymer;
The (4-aryl) piperidine monomer comprises N-methyl-4-trifluoroalkyl ketone piperidine or N-methyl-4-trifluoroaryl ethyl ketone piperidine.
8. The method for preparing the poly (4-aryl) piperidine polymer according to claim 7, wherein:
the molar ratio of the phenyl structural monomer Ar with the linear structure to the (4-aryl) piperidine monomer is 1: (1-1.5); and/or the number of the groups of groups,
the hydrophobic copolymerization unit R 1 The molar ratio of the corresponding ketone monomer to the (4-aryl) piperidine monomer is (0-0.5): 1, a step of; and/or the number of the groups of groups,
the first solvent comprises at least one of dichloromethane, chloroform or tetrahydrofuran; and/or the number of the groups of groups,
the second solvent comprises at least one of ethyl acetate, methanol, ethanol, diethyl ether, tetrahydrofuran or acetone; and/or the number of the groups of groups,
the volume ratio of the first solvent to the second solvent is 1: (10-30); and/or the number of the groups of groups,
the (4-aryl) piperidine monomer is added in an amount of 10-22.5mmol of the (4-aryl) piperidine monomer per 10-15mL of the first solvent based on the amount of the first solvent added; and/or the number of the groups of groups,
the first catalyst comprises trifluoroacetic acid (TFA) and/or trifluoromethanesulfonic acid (TFSA); wherein,
the molar ratio of the trifluoroacetic acid to the (4-aryl) piperidine monomer is (1-2): 1, a step of; and/or the number of the groups of groups,
The molar ratio of the trifluoromethanesulfonic acid to the (4-aryl) piperidine monomer is (10-20): 1, a step of; and/or the number of the groups of groups,
said step (1) further comprising the step of washing and/or drying said polymer; wherein,
the washing step comprises the step of adding a first alkali liquor for washing and the step of adding the first alkali liquor for washing; preferably, the primary lye comprises K 2 CO 3 KOH, naOH or NaHCO 3 At least one of the solutions, preferably at a concentration of 0.5-2.0M; and/or the number of the groups of groups,
the drying step includes a step of vacuum drying at 60-80 ℃.
9. A quaternized poly (4-aryl) piperidine polymer, characterized in that the polymer has a structure represented by the following formula (Q):
wherein Ar, R is 1 Is as defined in the poly (4-aryl) piperidine polymers of claims 1-6;
the R is 5 Comprising a group having a quaternized structure;
preferably, the method comprises the steps of,the R is 5 An alkyl chain comprising a quaternized structure;
preferably, said R 5 Comprising C1-C10 alkyl chains of quaternized structure.
10. A process for preparing a quaternized poly (4-aryl) piperidine polymer of claim 9 comprising the steps of taking a poly (4-aryl) piperidine polymer of claims 1-6 into a third solvent and adding a second catalyst and a corresponding structural haloalkane to effect quaternization, and adding a fourth solvent to mix and collect a precipitate, depending on the structure of the quaternized poly (4-aryl) piperidine polymer selected.
11. The method of preparing a quaternized poly (4-aryl) piperidine polymer of claim 10, characterized by:
the solid to liquid ratio of the poly (4-aryl) polymer and the haloalkane is 1g: (1-3) mL; and/or the number of the groups of groups,
the mass ratio of the poly (4-aryl) piperidine polymer to the second catalyst is (2-3): 1, a step of; and/or the number of the groups of groups,
the second catalyst comprises K 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,
the solid-to-liquid ratio of the poly (4-aryl) polymer and the third solvent is 1g: (10-20) mL; and/or the number of the groups of groups,
the third solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
the fourth solvent comprises at least one of ethyl acetate, methanol, ethanol, acetone or diethyl ether; and/or the number of the groups of groups,
the volume ratio of the third solvent to the fourth solvent is 1: (6-10); and/or the number of the groups of groups,
the temperature of the quaternization reaction is 40-60 ℃; and/or the number of the groups of groups,
the method further comprises a step of drying the precipitate, preferably the drying step comprises a step of vacuum drying at 60-80 ℃.
12. A high-stability anion exchange membrane is characterized in that the anion exchange membrane is OH - An anion exchange membrane having a structure represented by the following formula (T):
wherein Ar, R is 1 Is as defined in the poly (4-aryl) piperidine polymers of claims 1-6;
the anion exchange membrane is prepared from a starting material comprising the poly (4-aryl) piperidine polymer of any one of claims 1-6 and/or the quaternized poly (4-aryl) piperidine polymer of claim 9.
13. A method of making the high stability anion exchange membrane of claim 12 comprising the steps of:
(1) Adding the quaternized poly (4-aryl) piperidine polymer of claim 9 into a fifth solvent, mixing, casting on the surface of a substrate, and obtaining a polymer film;
(2) The polymer film is placed in a second alkali solution for immersion to obtain OH - And (3) an anion exchange membrane.
14. The method for preparing a high-stability anion exchange membrane according to claim 13, wherein:
the solid to liquid ratio of the quaternized poly (4-aryl) piperidine polymer to the fifth solvent is 1g: (10-100) mL; and/or the number of the groups of groups,
the fifth solvent comprises at least one of dimethyl sulfoxide, N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; and/or the number of the groups of groups,
The thickness of the polymer film is 20-60 mu m; and/or the number of the groups of groups,
the second alkaline solution comprises NaOH and/or KOH solution, and the preferable concentration is 0.5-2.0M; and/or the number of the groups of groups,
the temperature of the dipping step is 25-80 ℃ and the dipping time is 8-12h; and/or the number of the groups of groups,
the method further comprises the step of placing the anion exchange membrane in deionized water which is filled with a protective atmosphere for preservation.
15. A process for the preparation of a high stability anion exchange membrane according to claim 13 or 14, further comprising the step of preparing the desired quaternized poly (4-aryl) piperidine polymer according to the process of claim 10 or 11 with the poly (4-aryl) piperidine polymer of any one of claims 1-6.
16. Use of a high stability anion exchange membrane according to claim 12 for the preparation of an alkaline water electrolysis cell and/or an alkaline fuel cell.
17. An alkaline water electrolyzer, an alkaline fuel cell and/or an alkaline fuel cell device prepared from the high stability anion exchange membrane of claim 12.
18. Use of the poly (4-aryl) piperidine polymer of any one of claims 1-6 and/or the quaternized poly (4-aryl) piperidine polymer of claim 9 for the preparation of an anion exchange membrane.
19. Use of the poly (4-aryl) piperidine polymer of any one of claims 1-6 and/or the quaternized poly (4-aryl) piperidine polymer of claim 9 for the preparation of a catalytic layer coated anion membrane or gas diffusion electrode.
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